Ceramic cement



mo e,

cs P ASllG 1 I Patented Sept. 14,1943

"UNITED STAT Cross Reference CERAMIC CEMENT Willard K. Carter, Columbus, Ohio. assignor to National Alumin'a'te Corporation. a corporation of Delaware- Chicago, 11].,

' No Drawing. Application March 10,1941,

" 1 Serial No. 382,585

I ldClaimsQ (Cl. 16-6-55) The present invent-ion relates to improvements in ceramic cements, by which term it is intended to include ceramic products such as fired articles made from siliceous raw materials such as sihceous refractories, refractory clay products such as fire clay, firebrickand the like, ordinary argillaceous clay products, fired specialties such as talc and steatite bodies, as well as the self-hard-- ening cements such as are exemplified by Portland cement and its equivalents.

More particularly, the present invention relates to the employment of a special type of reagent to assist in the bonding of ceramic ware, using the term in .the above connotation, which material consists of a. colloidal aqueous solution of silica,

SiQz, which is oia high degree of purltyand contains 'very'little material other than SiO2', and water, and in which event the-ratio 9i Si'O: to NazOisatleastlOzl.

One ofthe'. objects of the invention therefore is to improve the manufacture of fired ceramic ware and unfired self-hardening cements by incorporating therewith, during some stage of their fabrication, quantities of a colloidal silica solution which greatly enhances the strength of the products and also endows them with other high:- ly desirableproperties The colloidal silica solution used for. the present purpose is one which is prepared by treating a diluted solution of an alkali silicate-with a carbonaceous base-exchange material which abstracts the alkalimetal ions therefrom, leaving the silica in stable colloidal solution. Somuch ofthe alkali metal salts. are removed from the silicate solution that the ratio of S102 to NazOymay be even as high as 50:1. Despite the fact that there is so little sodium salt left, the solution is quite stable and may be kept for a number of years even though it have a concentration of asmuch as solids. The solut'ion is a clear liquid having many remarkable properties which are particularly adapted to the purposes of the present invention. For more details relative to this colloidal silica solution, reference is directed to the application of Paul G. Bird, Serial No. 329,729, filed April 15, 1940, now matured into United States Patent No. 2,244,325, of June 3, 1941. This colloidal silica solution is now on the market as a commercial product, and for the sake of simplicity and in order definitely to designate theproduct utilized, I have coined therefor the fanciful name Colosil, by which I mean the product of the said Bird application and patent. 'I'his,Colosil is very slightly alkaall line reacting, but may be neutralized to phenol- 5o phthalein neutrality by means of a suitable acid without causing flocculation or precipitation of the therein contained silica. It may also be that the silica is really in the form of its hydrate, such for example as Si(OH)4. It should be thoroughly understood that the Colosll is entirely dissimilar to any previously known type of colloidal silica solution and is in ,nowise" to be confused with dilute solutions of alkali silicates or even the socalled'neutralized alkali silicates, because these invariably will contain the ions resultin from the neutralizing agents'and also will still contain, 1n undlminishedamount, thealkali metal, suchas' the sodium which was originally combined with silicic acid in the form of silicate. Such solutions of silicates possess altogether different properties from those of the Colosil and could not be substituted therefor.

, I- have discovered that by the use of the Cclosil it is possible to prepare materials which are of great benefit in a number of ceramic processes. These new materials or ceramic cements, as they might-be called, may truly be considered as constituting-a novel form of chemical compound. It will be obvious from the numerous examples given 'hereinbelow that the materials cannot be com sidered as true silicates, but at the same time it isevident. that there is some combination of silica which catalyzes or in some other way greatly accelerates the normal action of certain chemicals used in the ceramic arts. It'hence follows that the materials treated with Colosil' are in some way altered so asto become endowed with unique chemical properties. '1

.In ceramic processes such as those which involve the use .of highly siliceous materials the bonding is usually eifected at least in part by the fiuxing ofsilica from't-heceramlc body and the subsequent crystallization of such fiuxed silica in the form of a mineraILor. mineral combination which is advantageous with respect to the ultimate properties of the product; I have been able to, obtain direct and conclusive evidence that ceramic raw materials treated with Colosil react entirely differently than the untreated materials andthat such a. difference in reaction is not due to a simple enrichment ofthe body of the silica. This can be demonstrated conclusively by the use of, for example, calcium hydroxide or barium' aluminate; which either have been 'used con jointly-with or previously treated with Colosil. 'I'hus,.I.have among my examples ceramic bodies containing initiallynearly silica available for reaction with, ior example, calcium hydroxide, whichbehave quite differently if the calcium Examiner hydroxide be used conjointly with the Colosil, which could not be accounted for by the slight increase in silica content.

I have found it quite impossible to theorize about the new compounds or to determine their actual forms either as they exist when first mixed with the-ceramic rawmaterials or as they exist in the finished'product, but for the sake of cone venience I will term these new materials which have been treated with Colosil as the silicizedcement, silicized talc, and silicized magnesiumsalts.

The silicafication may be carried out in any manner most convenient to the particular process involved, the important essential being to effect sufiicient contact of the Colosil with the chemical which is to be silicized. This may involve the prior admixture of the Colosil with the chemicalto be treated, followed by the subsequent introduction of the newly formed silicized compound into a suitable ceramic batch or it may be accomplished satisfactorily by, for. example, mixing Colosil with a ceramic batch already containing the material which it is desired to silicize. The following examples give the detailed steps which I have used to accomplish the desired results in a number of processes.

EXAMPLE 1 "'SrLIcA RsrRAoroRms In order to establish the differences between my present invention and the prior art, I will now give examples in the case of silica refractories which have been made with the normal or hitherto used 'bonding materials as compared with silicized chemicals. The procedure of manufacture was in all cases the same. For example, lump ganisten-which contains about 99% SiOz, was charged into a wet pan type of mixer and grinder, wherein the silicized chemicals or the Colosil and chemicals to be silicized were added and the mixture groundcuntilthe ganister was reduced =toa size permitting hard moldingof the mixture. The granule size for this purpose is well known in the art of manufacturing .ganister refractories,--and the sizes may be, for example, those shown in McKinley and Carter Patent No. 2,017,723. The mixin each case was made byhammering into metal and a suitable bonding agent such as either barium aluminate or lime, making comparable batches both with and without the Colosil. The batches had the following composition:

Batch 1 Pounds Ganister 1 1300 3BaO.Al2O3 26 Water 145 Batch 2 I Pounds Ganister 1300 3Ba0.AlzOa 26 Colnsil 104 I SiO2 pounds 6.24 1 N12200: do .208 H2O do 97.56

Watery. 49

Batch 3' p i I Y I Pounds 'Ganister ;1; ';1 1300 Hydrated lime 18 Colosil 78 *SiOz -pounds 4.48 NaaCOa dO 0.156 H2O -do 73.36 Water -78 jBat h-4 A "-."P0l1lldS Ganister, ;-;1;1; e 1 11; 1300 lime Water "150 molds, the molds then being removed, dried at approximately 250 .F., and eventually fired- :in

suitable kilns to cone 20 (0mm). -11; must be Y realized that the chemicals added to' this essentially all silica body would .havea maximum opportunity for reaction with silica during nor-- mal heat treatment, andhen'ce the Colosil can not be considered as appreciably enriching-the bodyin silica. It can be assumed that any.dif-- ferencein reaction brought about by additionlof the Colosil must result from the-actual alteration of the characteristics of the chemical addi-' tion and that this alteration is induced by the combination ofthe material with Colosil, which combination I choose to termsilicafication.

Therefore, in order to demonstrate from this point of view the advantage, of the use of ColosiL- I have hadprepared four. difierent batches of highly siliceous refractory based upon .gamster 'No attempt was made to process a mix similar to Batch 3 containing only 1% of lime without the Colosil addition, because previous commercial experience had demonstrated that it is impossible to obtain ware good enough for testing with so small an addition of lime; -'It should be particularly noticedthat the 'Colosil additions used are in the range where'silica additions thus supplied cannot result in mixtures comparable in ultimate "analysis to-any known natural or available silicates of the chemicals concerned." In the present 'set of examplesthefsilicafication-was accomplished by mixing the chemical additions (such as the barium alumin'ate or hydrated lime) with'the Colosil prior to the addition thereoito the ganister batch. P In the above set of bat'ches; Batch "4 corresponds to an example of well-known prior regular commercial practice, and it is included in order'to determine how closely the properties of a mixturecontaining only -1%- of silicized lime would compare withj'normal practice using 2% ofordinary lime. 9 'fThe physical properties 'oi'gtheprodiicts obtained are illustrated in Table'l hereinbelo'w:

j .f Table [if PHYSICAL-BROPERTIES-STLNDARDi'IESTS v Batch 3, Batch 4,: Batch 1, silicized Ordinary "Barturn mm lune lime aluminate aluminate hydrate, hydrate,

Percent porosity' 31.7 30.7 27.4 27.0 App.sp.gr 2. 3l 2.30 2.30.; '-2. 30 131k. density I 1.58 1,60 1.67 1.67 P.C."E. 31. 32 31.32 31.32 31. 32 Loedtest (A)- -.F 2630 It-2690' 0.0% 0 Reheat 8-0. 07% 0.'25% S-0. 04% S 0. 01% Mod. of rupture"; 450 630# 1380i. 1100# i 36. COtlPOS TlONS,

R PLASTIC Spelling tests have shown that silicarefractories bonded with lime and Colosil are superior to those bondedvwith lime alone with respect to spelling, resistance. It has been found that if these brick are heated up to-1470 FL; employing varying time intervals for theheating-up period, the more rapid the rate of heating the greater the percentage of brick which will crack during the heating-up and cooling periods;- Batch 1- brick (containing no Colosil) all cracked when heated to 1470" F. when employing90 minutes, 100 minutes, and llominutes for the heating-up intervals, while Batch 3 brick showed much less tendency to crack during comparative treatment of the latter, and -11v r.

Employing the 90 min. interval-80% cracked, Employing the 100 min; interval-60% cracked l Employing the 110 min. interval40% cracked v From this table it will be noticed thatall DIOD-r erties are approximately equal, except the strength, which is reatly improved in Batch 3, which it will be noticed has a modulus of rupture as high as. 1380 pounds. It was also round that when the refractories containing the silicized material were placed into service under conditions involving periods or intermittent heating close to or even above their fusion point there was much less dripping loss and deterioration by reason of less fillX.- In the case of the silicized barium aluminate there was an increase in" strength, but therewere also other important considerations which are not so apparent merely by inspection of the table.

The workmen who prepared these commercial size batches 1 and 2; containing ordinary barium aluminate and silicized barium aluminate'said' that Batch lwas somewhat difficult tohandle, as, it had definite thixotropic properties; become ing more fiuid when WQ IKGd so that the brick showed a tendency to slump under their own weight. After these brick had been dried it .was found that some of the dried barium aluminatet had migrated to the dryingsurfaceau In con trast thereto, Batch 2, containing silicized barium aluminate, readily-formed: a firm nonslumping brick, drying with no orvvery slight evidenceaof migration of the barium aluminate.

Ware set in the bottom or the kiln for. firing, where it has to support a considerable load during the burning, showed slight distortion in Batch. 1 but none in Batch 2. This reactloneis a very important manufacturing improvement.

The batches containing lime and silicized lime behaved normally during the entire processing procedure I r v ,The foregoing tabletherefor'e shows the influence of silicafication on chemicals known to reactwith silica in batches containing essentially; nothing. butlsilicahr The sodium content, introducedwith the Colosil, was so slight that its 0011;;

Cross Reference sideraticn may be neglected. Any appreciable addition at sodium would have reflected itself by decreasing the load bearing value and the pyrometric cone equivalent The eflect of the Colosil addition therefore is just the opposite. Microscopic examination or the fired pieces otfered still iurtherecidence that the silicized chemicals produoed a diflerent reaction. Concerning the fired mixtures, a competent petrographer stated:

'Ihemicroscopie examination or these mixtures has in general indicated several pertinent t I EXAMPLE 2 Fm: Cu RnFiucToRms The method of using sodium aluminate as a bonding agent for high-grade fire clay refrac-, toiies has already been describedin the prior art for example in earlier Patents Nos. 2,019,618; 2,019,619. and 2,102,327, in which I am a joint inventor-and is operating as a successful process. I have found, however, that this sodium aluminate' process is notuniversally applicable. The true reason for this I have never, been able to determine; and I believe that the variations in results are probably attributable to the physical nature of the clays derived fromdifferent' locations I have discovered that if I sili'cize the sodium aluminate or use it conjointly with'the Colosil, I can make this process applicable to advantage even to those clays which have not responded to the sodium aluminate treatment" These silicized forms'oi sodium aluminate, namely, the compounds formed by reacting sodium alur'ninate with Colosil, are not to be confused with thezeoiite'type of compounds which are formed by the double precipitation of an alkali silicatesuchjassodium' silicate with sodium alumin-ate. In fact; the Colosil, when added to a sodium aluminate solution; does not produce a gel or any product having the characteristics of the products'produced by mixing an alkali silicate with'an alkali'aluminate. The silicized alinninates, however, are much more refractory materials which in; themselves will not fuse at. the. temperatures 'which they encounter in the firing processes to which the ceramic products are sublectcd during their manufacture. In other words, it appears that the silicized aluminate compounds musttak'e up some other ceramic constituent from the body of the ceramic material, combining therewith by fusion and thereby producing a fired bond. It is known that sodium aluminate by itseli is a very refractory material (cone 38-40)} but it is usually activated because it is -always used" in the wet form, thereby liberating suflicient sodium hydroxide to initiate'sonie attack onthe siliceous constituent of the ceramic body and thereby initiating fusion of newlyformed. lower melting products; The

ability ofthes initial fusions to take alumina Examiner to function as desired. If these fusions take alumina into combination and reprecipitate it as mullite in the bonding glass or at grain boundaries then it may be presumed that the ultimate bodywill be stable with respect to volume changes on reheating in service and that its spalling resistance will be high. If the alumina content of the aluminate does not go into combination but remains as an inert dispersed alumina hydrate residue, it is quite likely that the addition will have no effect on reheat volume stability or spalling characteristics.

This leads to the most important distinction between silicized aluminate and any other known type of alumina-silica mixture. Sodium aluminate may be heated with silica or a clay and a glass developed showing no evidence of mullite. silicized aluminate used to develop a glass through heating a batch of identical composition will develop mullite. In the most simple terms, silicized aluminate is a compound extremely activated with respect to ability to bring about a fusion combination of alumina with silica during heat treatment.

As examples of utilizing these silicized aluminates, I prepared two different types containing different ratios of sodium aluminate to Colosil, which I have designated SSA-'1 and SSA-2Q meaning silicized sodium aluminate No. 1 and No. 2. SSA-1 was formed by mixing 205 grams of sodium aluminate (80% NazQAlzOs and 20% H20) and 250 grams of Colosil (6% S102). The approximate molal composition thus produced would be 4Naz0.4AlzOa.SiOz. This SSA-l forms a clear liquid which when spread out will dry in a thin film without shrinkage. It has high adhesive strength when dry and may be dried and fired without encountering any decrease in adhesive strength. Nonplastic ceramic materials may be bonded with this material and subjected to any heat treatment below the fusion point of the nonplastics themselves without danger of loss in strength during the dehydration stage, and refractories thus bonded need not even be prefired before being placed into service.

Having prepared the SSA-1, I then prepared the following batch: 95% by weight of calcined clay and 5% by weight of SSA-1. This mixture was shaped and dried, and when fired it would not fuse even though fired to cone 35, although mullite development was noticed at as low as cone 15. This mixture has great penetrating ability and may be used, for example, for impregnation of prefired fire clay refractories as a hardening agent and to prevent their warping and cracking when in service. When such impregnated refractories are fired in service, impregnation with the SSA-1 produces a high degreeof mullite formation, and this, crystallization acts as a stifiem ing and bonding medium to increase the load bearing ability and to prevent cracking. The SSA-1 mixture may also be employed as. animpregnating material for refractories which are bonded with calcium aluminate cements. It is well known that such cement bonded mixtures (without the Colosil) will normally soften and tend to disintegrate at about 1500? F., so that their satisfactory use is limited to serviceslnot exceeding this temperature. However, if these refractories are manufactured with SSA-1, their strength even in the 1500 range is maintained by the rigidity of the impregnation at a level which is only slightly under cold-set strength.

Consideration of the properties of this 'SSA- material should serve to illustrate that this form of silicized sodium aluminate is in no way similar to any form of sodium aluminate of earlier days. More intense silicafication of sodium aluminate bythe use of larger quantities of Colosil produces materials of a lower solids content which become somewhat more viscous in character as the colloidal silica content is increased. B'y reason of their lower solids content, however, their adhesive characteristics decrease as the silicafication treatment increases. As an example of such a higher silica compound, I may mention SSA-2, formed by mixing 205 grams of sodium aluminate and 1000 grams Colosil. This material will fuse at cone 18, and the fusion will show clear mullite development. It is more viscous than the 88-1 and does not have its penetrating ability.

In fire clay refractories the matter of determining the most suitable silicized compound to be used and the best quantity of addition is a problem which must be solved by empirical experimentation. The following is an example which will serve to illustrate a suitable method of such investigation and also will serve to illustrate the comparable results obtained with the silicized aluminate-on the one hand and normal or ordinary sodium aluminate on the other hand:

Materials Kentucky flint fire clay Pyrometric cone equivalent-34 Sodium aluminate-normal SSA14N9.20.4Al203SiO2 f SSA2NazO.A1zOa.'SiOz Silicafication accomplished by Colosil in all cases.

Procedure (1)- Grind, temper with water and mix flint in a dry pan to desired size in combination with semi-flint clay. (P.-C. E. 32-33.)

Batch:

. flintcone 34 l 5% semi-flint-cone 32-33 (.2) Remix'in batch mixer 1 I (3) Press to brick size ontoggle press r (4) Dry and fire to cone -12.

Improvement desired Chemical additions made (in the initial wet pan grinding) 1. No chemical added 2. 0.5% sodium aluminate 3. 0.5% SSA-14Na2O.4Al2O3.SiO 4. 0.75% SSA-1-4NazO.4A12O3.SiO2 5. 0.50% SSA2Na2O.A12O3.SiO2 6. 0.75% SSA-2-Na2O.AlzO3.SiO2 SSA-l: 1',

. .Na20.Al203-.-91.6%

.Na2O.AlzO3-73.3

SiO2-26.'I%

I Reheat values-130050.

1 per cent 2.4 2 do 2.4 3-

do i'0.9 ..d0.. 0.9 5 .do .0.7

6 1 f 'do '..'..0.4

3G6. COfiPOSiTlONS,

COA'IENG UR PLASTIC Nfo; 6 was selected for commercial production. Following are complete physicalspecifications obtained comparedwith normal and sodium The increased weight of, these. refractories is attributed to the lubricating action of the viscous sili'cize'd aluminaite'; It' does not influence in herent reheat characteristics.

The above data should serve to illustrate clearly the influence ofColosil" 's'ilicafication on the sodium aluminate reaction; Mix No. 5 contains less aluminate than mix No. 2 and mix No. 6 approximately the same quantity.

While the foregoing constitute the more im-- portant examples of the use of silicized materials in connection with refractories, I have also found that silicized products are useful in other connections. 'IhusQ for example, silicized precipitated calcium carbonate possesses very valuable and peculiar properties which make it particularly applicable to paper coating or as a filler in oil paints. It could hardly have been expected that a colloidal" silica solution would react with ordinary calcium carbonate, as it is known that diluted sodium silicate solutions definitely will not react with calcium carbonate. However, I have performed a number of experiments with Colosil-w'ater solutions in which I have suspended and agitated precipitated chemically pure calcium carbonate for the same period of time, followed by filtration of the material on a suction filter so as to remove all free liquid. The filtrate analysis and the filter cake were then dried to determine what took place. The following mixtures were made: 7 1

Mix 1- 50 cc. Colosil+450 cc. of water (H20)+100 gms. CaCO;- Mix 2l00 cc. Colosil-HOO cc. of water (H2O)+1OO gms. CaCO; Mix 3-l50 cc. Colosil+350 cc. oi wal'el' (H'zOH-IUO gins.- Mix 4500 cc. Colosii-i-No cc. o1watei' (HO)+l00 gins. M ix 5'-No cc. Colosil-l-SQOcc. 01' water (Hi) +100 g ns. A,

The liquid portion ofthe above mixes contained the following solids per cc.-- q w Mix L m" .0062 Mix 2 gm .0124 Mix 3- w em .0186 Mix 4 gm .0620 Mix None The following time was required for filtration:

Mix 1. 13 min. Mix 2 15 min. Mix 3 24 min. Mix 4 18 min. Mix 5 2 min., sec.

Drying of the fitler cakes showed that the following amounts of liquid were not removed by filtration:

Mix 1 Mix 2 Mix 3 Mix 4 Mix 5 Cross Reference Volume of filtrates andsolids content per cc. (obtained by evaporationit Mix 1-415 CcIiiltered 0E. containing .0035 gins. solids per cc.

Mix 2-415 00. filtered off, containing .0090 gins; solids per cc.

Mir 3-434 cc. filtered 06, containing .0145 gms. solids per cc. Mix 4-412 cc. filtered oli. containing .0558 gins. solids per cc.

Mix 5-392 cc. filtered oil, containing no solids The following shows the solids content of the original liquids compared with that of the liquids after reaction'with the carbonate:

I After reaction Solids Original reacted 1 The calcium carbonate masses resulting from mixes 1', 2-, 3 and 4 filtered to compact, coherent masses, while mix 5 remained mushy. After drying, the masses resulting front mixes I to 4 exhibited brittleness and strength, which was missing-in mix 5. A sodium silicate solution having a ratio of 173.25; diluted so as to obtain the same silica molality as the Golden, exhibited no evidence'whatever of combining can the calcium' carbonate.

The calcium carbonate thus mademay'be dried and ground and-ls a far more effective filler or coating material for paper than ordinary calcium'carbonate. It may, or course, also be combined with various ceramic-materials if desired.

EXAMPLE 5 Another ceramic bonding material which I have found very advantageous consists of 200 parts of sodium aluminate and253 parts of Colosil solution containing 6% of SiOz. The mixture is a clear liquid and may be used as indicated hereinabove in connectionwith Examples 2and3. EXAMPLE 6- The Colosil" may also be employed; as-already indicated; as a valuable addition to hydraulic cements; producing therein a much more uniform gelation, which increases the water retention of the cement. For example, if 15 parts of Portland cement or the like are mixed with parts of limestone or similar aggregate, the addition of Colosil to the tempering water will effect a gelation of the cement which is beneficial from two standpoints: (1) this gelled-cement water mix will adhere to and cover the aggregate more uniformly and (2) its gelatinous character will result in the better packing of the aggregate. It is well known that mixtures of cement and aggregate are often flowed or poured into place; and if water alone is used as the tempering medium, the amount of water required to produce adequate flow is sufiicient to wash the cement from Examiner 

